Studies on Molecular Devices showing Redox Response

本课题旨在构建具有电致变色等电化学反应的有机氧化还原体系。为了实现这样的分子体系，采用了一种新的分子设计方法，其中：(1)带电物质将通过形成具有大π共轭的强发色团而不是芳构化来稳定；(2)在电子转移过程中应该发生剧烈的结构变化。这些条件与长期以来用于多级氧化还原系统设计的条件有很大不同。“动态氧化还原行为”是这项工作的核心概念，因此设计了氧化还原对，以便在电子转移时进行可逆的C-C键形成和裂解。以含环烷烃环的二苯并ttf衍生物及其三环骨架异构体为原型进行了详细的研究。这里的一些分子研究被证明是可逆的动态氧化还原系统。为了构建电致变色体系，设计了含有三芳基甲烷染料骨架的其他分子。证明了六芳基乙烷衍生物与二（三芳基甲烷）指示物之间的可逆相互转化。

The research project is intended to construct the organic redox systems which exhibit the electrochemical response such as electrochromism. In order to realize such molecular systems a new way of molecular designing was adopted where (1) the charged species would be stabilized by formation of strong chromophores with large pi-conjugation but not by aromatization and (2) drastic structural changes should be occurred during the electron transfer. These conditions are quite different from what had been used to design the multi-stage redox systems for a long time. The "dynamic redox behavior"is the central concept in this work, thus the redox pairs were designed so as to undergo reversible C-C bond formation andcleavage upon electron transfer. Dibenzo-TTF derivatives inserted with a cycloalkane ring as well as their isomersof the tricyclic skeleton were studiedin detail as prototypes. Some molecules studies here were proven to be thereversible dynamic redox systems . In orderr to construct the electrochromic systems other molecules containing triarylmethane dye skeletons were designed. The reversible interconversion between hexaarylethane derivatives and bis (triarylmethane) dications was demonstrated .